CN103288676B - Preparation method of cyclohexanone-oxime - Google Patents
Preparation method of cyclohexanone-oxime Download PDFInfo
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- CN103288676B CN103288676B CN201210049463.8A CN201210049463A CN103288676B CN 103288676 B CN103288676 B CN 103288676B CN 201210049463 A CN201210049463 A CN 201210049463A CN 103288676 B CN103288676 B CN 103288676B
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Abstract
The invention provides a preparation method of cyclohexanone-oxime, which is implemented in a way that: under reaction conditions of cyclohexanone ammoximation, a reaction raw material containing cyclohexanone, ammonia, hydrogen peroxide and solvent passes through a plurality of catalyst bed layers in a fixed-bed reactor; each catalyst bed layer contains a titanium-silicon molecular sieve and resin; in the flow direction of the reaction raw material in the reactor, the resin content in the catalyst bed layer increases progressively; and the weight percent of at least part of resin in the catalyst bed layer is less than 50%. The preparation method provided by the invention can obtain higher cyclohexanone conversion rate and cyclohexanone-oxime selectivity.
Description
Technical field
The present invention relates to a kind of preparation method of cyclohexanone-oxime.
Background technology
Cyclohexanone-oxime is the key intermediate of synthesis of caprolactam, is a kind of important industrial chemicals, mainly as the raw material of feedstock nylon 6 monomer preparing fiber and nylon 6 and engineering plastics.
Because titanium-silicon molecular sieve catalyst has very important effect in organic compound selective oxidation, therefore, as the preparation method of cyclohexanone-oxime, propose under the existence of titanium-silicon molecular sieve catalyst, utilized hydrogen peroxide and ammonia to carry out oximes method to pimelinketone.In the past the advantage of this method does not need, as carried out the method for oximate with oxammonium sulfate, to utilize ammonia neutralisation of sulphuric acid.
In the process of preparing cyclohexanone oxime by ammoximation of cyclohexanone, titanium-silicon molecular sieve catalyst shows excellent shape selective catalysis performance, general particle diameter is less, catalyst activity is higher, selectivity is better, in practical application, the particle diameter of titanium-silicon molecular sieve catalyst is about 0.1-15 μm, but, particle diameter little like this brings great difficulty with being separated of product can to catalyzer, although the existing various achievement in research about filtering material is applied in actual production, but for being separated of titanium-silicon molecular sieve catalyst and product, the resistance produced when it filters also does not lie in the size in the duct of filtering material, but come from superfine little catalyst particle and occupy and block the duct of formed filter cake, especially the particle diameter catalyst particle that is less than 2 μm is the most unfavorable to filtration, cause production efficiency low like this, also the process of HTS industrial applications is had influence on.
For this reason, after normally former for HTS powder being added tackiness agent through spray shaping be granularity between 5-100 μm, mean particle size be 20 μm after use, such as, have in the documents such as EP0384390, EP0311983 and EP0496385 and disclose relevant technique.But these use the technique of shaping HTS to there is following problem: the use of tackiness agent in the shaping of HTS and moulding process, not only causes the loss of HTS, and there is impact to the pore volume of catalyzer and specific surface area.
In order to the defect that the technique solving the shaping titanium-silicon molecular sieve catalyst of above-mentioned use exists, CN102311363A proposes in fixed-bed reactor, uses the cyclohexanone oxamidinating technique of composite catalyst as catalyzer of HTS and resin.But, in actual production process according to the method for this patent application, due to resin content in beds too high (being generally 50-99 % by weight), make the selectivity of the transformation efficiency of cyclohexanone oxamidinating process cyclohexanone and cyclohexanone-oxime all lower.
Summary of the invention
The object of the invention is, in order to overcome in existing cyclohexanone oxamidinating process the above-mentioned defect existed, to provide a kind of preparation method of new cyclohexanone-oxime.
The invention provides a kind of preparation method of cyclohexanone-oxime, the method comprises: under cyclohexanone oxamidinating reaction conditions, make the reaction raw materials containing pimelinketone, ammonia, hydrogen peroxide and solvent by the multiple beds in fixed-bed reactor, each beds is all containing HTS and resin, along the flow direction of described reaction raw materials in reactor, in described beds, the content of described resin increases progressively, and described at least part of described beds, the weight percentage of resin is less than 50%.
The preparation method of cyclohexanone-oxime according to the present invention can obtain higher pimelinketone transformation efficiency and cyclohexanone-oxime selectivity.
In addition, the present invention also has the following advantages:
(1) there is not the problem that catalyzer and reaction product are difficult to be separated in described method of the present invention;
(2) in the present invention, HTS is shaping without the need to carrying out, thus avoid cause in moulding process HTS loss and make HTS lose amount of activated problem.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The preparation method of cyclohexanone-oxime according to the present invention comprises: under cyclohexanone oxamidinating reaction conditions, make the reaction raw materials containing pimelinketone, ammonia, hydrogen peroxide and solvent by the multiple beds in fixed-bed reactor, each beds is all containing HTS and resin, along the flow direction of described reaction raw materials in reactor, in described beds, the content of described resin increases progressively, and described at least part of described beds, the weight percentage of resin is less than 50%.
A preferred embodiment of the invention, along the flow direction of described reaction raw materials in reactor, the total height that the weight percentage of described resin is less than the beds of 50% is 5 ~ 90% of the total height of described beds, be more preferably 10 ~ 80%, more preferably 20 ~ 60%.
Preferred, along the flow direction of described reaction raw materials in reactor, the height of every layer of described beds is 0.5 ~ 95% of the total height of described beds, is more preferably 2 ~ 50%, more preferably 10-40%.
According to another kind of preferred implementation of the present invention, along the flow direction of described reaction raw materials in reactor, described in adjacent two beds, the difference of the content of resin is 5 ~ 50 % by weight, is more preferably 10 ~ 30 % by weight.
In the present invention, HTS in each beds and the content of resin can change within a large range, under preferable case, along the flow direction of described reaction raw materials in reactor, the content of resin described in first beds can be 5-30 % by weight, and the content of described HTS can be 70-95 % by weight; The content of resin described in last beds can be 70-99 % by weight, and the content of described HTS can be 1-30 % by weight.
In the present invention, there is no particular limitation for the number of described beds, but, when the number of described beds increases gradually, although the transformation efficiency of cyclohexanone oxamidinating reaction process cyclohexanone can be improved gradually, but beds number increase the production difficulty that also can increase beds, and the regeneration difficulty of this beds.Therefore, consider the described cost of cyclohexanone oxamidinating technique and the transformation efficiency of pimelinketone, described catalyst bed preferably has 2 ~ 20 beds, more preferably has 3 ~ 10 beds.
In the present invention, described HTS can be the various HTS that this area routine uses.In the preferred case, described HTS contains Ti-MWW molecular sieve.In the preparation method of described cyclohexanone-oxime of the present invention, when described HTS contains Ti-MWW molecular sieve, the pimelinketone transformation efficiency and cyclohexanone-oxime selectivity that significantly improve can be obtained.
Preferred, in described HTS, the content of Ti-MWW molecular sieve is more than 10 % by weight, more preferably more than 50 % by weight.
In the present invention, described Ti-MWW molecular sieve can be commercially available, and also can prepare.The preparation method of described Ti-MWW molecular sieve such as can with reference to CN1686795A.
Under above-mentioned preferable case, except described Ti-MWW molecular sieve, other HTS that described HTS can also use containing this area routine, such as, HTS, the HTS of MEL structure, the HTS, ZSM-12 type HTS etc. of BETA structure of MFI structure.In described HTS, the content of other HTS described can be 0-90 % by weight, is preferably 0-70 % by weight, is more preferably 1-50 % by weight.
In the present invention, described resin can react and the resin not affecting the catalytic activity of described HTS for the various cyclohexanone oxamidinating that do not affect.Under preferable case, described resin is the polymkeric substance of vinylbenzene and polyene-based compound.Preferred, the weight ratio of vinylbenzene and polyene-based compound is 2-5: 1.Described polyene-based compound most preferably is divinylbenzene.
In the present invention, described beds contains HTS and resin, also the i.e. catalyzer that uses of the present invention composite catalyst that is HTS and resin.This composite catalyst can prepare according to the method for routine, its preparation method such as can comprise: under the existence of initiator, by HTS powder, the polymer monomer preparing resin and perforating agent contact reacts, obtain blocks of solid catalyzer, then by this blocks of solid catalyst breakage, and by swelling for the granules of catalyst obtained after fragmentation, then carry out extracting with extraction solvent.Concrete, described catalytic condition can comprise: temperature is 60-100 DEG C, and the reaction times is 1-20 hour.Described polymer monomer can be the mixture of vinylbenzene and polyene-based compound, and the weight ratio of vinylbenzene and polyene-based compound preferred 2-5: 1.Described initiator can be peroxide initiator or azo-initiator, and described peroxide initiator can be such as benzoyl peroxide, and described azo-initiator can be such as azo two isopropylcarbinol.The consumption of described initiator can be such as the 0.1-2 % by weight of described polymerization single polymerization monomer gross weight.Described perforating agent can be such as gasoline, C
5-C
13normal paraffin and C
4-C
12at least one in fatty alcohol.The particle size of the granules of catalyst obtained after the condition optimization of described fragmentation makes described fragmentation is 0.1-5 millimeter (being preferably 1-3 millimeter).Described swelling method such as can comprise the catalyzer obtained after fragmentation to be added in halohydrocarbon (as 1,2-ethylene dichloride) carries out swelling 1-20 hour.The condition of described extracting can comprise: temperature is 30-60 DEG C, and the time is 2-20 hour.And described extracting can repeat repeatedly, as 2-5 time.Described extraction solvent can be such as at least one in benzene,toluene,xylene, ethyl acetate, butylacetate, ethanol and butanols.
In the present invention, there is no particular limitation for the condition of described cyclohexanone oxamidinating reaction, can implement by reaction conditions conveniently, such as, described cyclohexanone oxamidinating reaction conditions can comprise: temperature of reaction is 55-95 DEG C, and reaction pressure is 0.1-0.5MPa, and during liquid, volume space velocity is 0.1-1h
-1.Here, described reaction pressure refers to absolute pressure.
In the present invention, in described reaction raw materials, the mol ratio of hydrogen peroxide and pimelinketone can be 0.8-1.5: 1, and the mol ratio of ammonia and pimelinketone can be 1.8-2.8: 1, and the volume ratio of pimelinketone and described solvent can be 1-10: 1.Hydrogen peroxide adds with the form of hydrogen peroxide usually, and hydrogen peroxide can add according to the concentration used conventional in industry.Ammonia can add with the form of ammoniacal liquor, also can add with the form of gas.
In the present invention, described solvent can be all kinds of SOLVENTS that this area routine uses, such as, can be methyl alcohol, ethanol, propyl alcohol, the trimethyl carbinol etc.A preferred embodiment of the invention, when described HTS contains Ti-MWW molecular sieve, when particularly containing the Ti-MWW molecular sieve of more than 50 % by weight, uses water as solvent.In this preferred implementation, not only can obtain higher pimelinketone transformation efficiency and cyclohexanone-oxime selectivity, but also collection process and the last handling process of cyclohexanone-oxime can be simplified, make the environmental protection more of whole reaction process.
The invention will be further described by the following examples.
The Ti-MWW molecular sieve used in following examples prepares according to the method for embodiment in CN1686795A 1.
In the examples below, pimelinketone transformation efficiency and cyclohexanone-oxime selectivity can calculate according to following calculating formula.
Mole number × 100% of the pimelinketone of pimelinketone transformation efficiency=(molar weight of the molar weight-product cyclohexanone of the pimelinketone of charging)/charging
Molar weight/(molar weight of the molar weight-product cyclohexanone of the pimelinketone of charging) × 100% of cyclohexanone-oxime selectivity=product cyclohexanone oxime
Wherein, the data acquisition of pimelinketone and cyclohexanone-oxime obtains with gas-chromatography (Shimadzu GC14B, DB-1 capillary column 30m × 0.25mm × 0.25 μm) analysis.
Embodiment 1
The present embodiment is for illustration of the preparation method of described cyclohexanone-oxime of the present invention.
(1) composite catalyst is prepared
In polymerization reaction kettle, add Ti-MWW molecular sieve powder, vinylbenzene, divinylbenzene and gasoline, after being uniformly mixed, during warming-in-water to 60 DEG C, add benzoyl peroxide, react 6 hours at 90 DEG C, obtain block composite catalyst, then carry out fragmentation and obtain the composite catalyst particulate that particle size is 1-3 millimeter, then 250 milliliters 1 is added, carry out swelling in 2-ethylene dichloride, keep swelling 5 hours at normal temperatures, pour out 1 afterwards, 2-ethylene dichloride, the ethyl acetate adding 200 milliliters again carries out solvent extraction, extraction temperature is 55 DEG C, extraction times is 4 hours, repeat extracting three times, obtain the composite catalyst of HTS and resin.
Prepare the composite catalyst A1-A3 of HTS and resin respectively according to aforesaid method, and in respective preparation process, the charging capacity of material is as shown in table 1 below.
Table 1
| Composite catalyst A1 | Composite catalyst A2 | Composite catalyst A3 | |
| Ti-MWW molecular sieve powder | 100g | 60g | 10g |
| Vinylbenzene | 20g | 50g | 100g |
| Divinylbenzene | 10g | 20g | 20g |
| Gasoline | 15g | 35g | 60g |
| Benzoyl peroxide | 0.5g | 1.1g | 2g |
(2) cyclohexanone-oxime is prepared
Successively composite catalyst A3, composite catalyst A2 and composite catalyst A1 being filled in diameter is 20 millimeters, length is in the fixed-bed reactor of 1200 millimeters, total filling volume is 50 milliliters, and the filling height ratio of composite catalyst A3, composite catalyst A2 and composite catalyst A1 is 1: 1: 1.Then, reaction raw materials (being made up of pimelinketone, hydrogen peroxide, ammonia and water) is injected fixed-bed reactor, reaction raw materials is flowed along the direction by composite catalyst A1 to composite catalyst A3, carry out cyclohexanone oxamidinating reaction, wherein, material rate is: the mol ratio of hydrogen peroxide and pimelinketone is 1.2: 1, and the mol ratio of ammonia and pimelinketone is 2.3: 1, and the volume ratio of pimelinketone and water is 5: 1; Reaction conditions is: temperature is 90 DEG C, and absolute pressure is 0.3MPa, and the volume space velocity of pimelinketone is 0.5h
-1.After successive reaction 100 hours, by analysis and calculate, pimelinketone transformation efficiency is 99.1%, and cyclohexanone-oxime selectivity is 99.5%.
Comparative example 1
(1) composite catalyst is prepared
Method according to embodiment 1 prepares composite catalyst, difference is, in preparation process, the TS-1 HTS powder of identical weight (purchased from Yueyang Effect of Catalysis In Petrochemistry agent factory) is used to replace Ti-MWW molecular sieve powder respectively, thus obtain composite catalyst D1 respectively, D2 and D3, wherein, in the preparation process of composite catalyst D1, in the add-on of TS-1 HTS powder and the preparation process of composite catalyst A1, the add-on of Ti-MWW molecular sieve powder is identical, in the preparation process of composite catalyst D2, in the add-on of TS-1 HTS powder and the preparation process of composite catalyst A2, the add-on of Ti-MWW molecular sieve powder is identical, in the preparation process of composite catalyst D3, in the add-on of TS-1 HTS powder and the preparation process of composite catalyst A3, the add-on of Ti-MWW molecular sieve powder is identical.
(2) cyclohexanone-oxime is prepared
Successively composite catalyst D3, composite catalyst D2 and composite catalyst D1 being filled in diameter is 20 millimeters, length is in the fixed-bed reactor of 1200 millimeters, total filling volume is 50 milliliters, and the filling height ratio of composite catalyst D3, composite catalyst D2 and composite catalyst D1 is 1: 1: 1.Then, inject reaction raw materials according to the method for embodiment 1 and control reaction conditions, and the flow direction of reaction raw materials is for flow to composite catalyst D3 by composite catalyst D1.After successive reaction 100 hours, by analysis and calculate, pimelinketone transformation efficiency is 86.5%, and cyclohexanone-oxime selectivity is 89.3%.
Comparative example 2
(1) composite catalyst is prepared
Method according to embodiment 1 prepares composite catalyst, and difference is, in preparation process, Ti-MWW molecular sieve powder adds 57g, and vinylbenzene adds 57g, and divinylbenzene adds 17g, gasoline adds 33g, and benzoyl peroxide adds 1.2g, thus obtained composite catalyst D4.
(2) cyclohexanone-oxime is prepared
Composite catalyst D4 being filled in diameter is 20 millimeters, and length is in the fixed-bed reactor of 1200 millimeters, and total filling volume is 50 milliliters.Then, inject reaction raw materials according to the method for embodiment 1 and control reaction conditions.After successive reaction 100 hours, by analysis and calculate, pimelinketone transformation efficiency is 92.1%, and cyclohexanone-oxime selectivity is 95.8%.
Comparative example 3
(1) composite catalyst is prepared
Method according to comparative example 1 prepares composite catalyst, and difference is, in preparation process, TS-1 HTS powder adds 57g, and vinylbenzene adds 57g, and divinylbenzene adds 17g, gasoline adds 33g, and benzoyl peroxide adds 1.2g, thus obtained composite catalyst D5.
(2) cyclohexanone-oxime is prepared
Composite catalyst D5 being filled in diameter is 20 millimeters, and length is in the fixed-bed reactor of 1200 millimeters, and total filling volume is 50 milliliters.Then, inject reaction raw materials according to the method for embodiment 1 and control reaction conditions.After successive reaction 100 hours, by analysis and calculate, pimelinketone transformation efficiency is 77.5%, and cyclohexanone-oxime selectivity is 79.8%.
Embodiment 2
The present embodiment is for illustration of the preparation method of described cyclohexanone-oxime of the present invention.
(1) composite catalyst is prepared
In polymerization reaction kettle, add Ti-MWW molecular sieve powder, TS-1 HTS powder, vinylbenzene, divinylbenzene and amylalcohol, after being uniformly mixed, during warming-in-water to 60 DEG C, add azo two isopropylcarbinol, react 6 hours at 100 DEG C, obtain block composite catalyst, then carry out fragmentation and obtain the composite catalyst particulate that particle size is 1-3 millimeter, then 250 milliliters 1 is added, carry out swelling in 2-ethylene dichloride, keep swelling 5 hours at normal temperatures, pour out 1 afterwards, 2-ethylene dichloride, the dimethylbenzene adding 200 milliliters again carries out solvent extraction, extraction temperature is 55 DEG C, extraction times is 4 hours, repeat extracting three times, obtain the composite catalyst of HTS and resin.
Prepare the composite catalyst A4-A7 of HTS and resin respectively according to aforesaid method, and in respective preparation process, the charging capacity of material is as shown in table 2 below.
Table 2
| Composite catalyst A4 | Composite catalyst A5 | Composite catalyst A6 | Composite catalyst A7 | |
| Ti-MWW molecular sieve powder | 60g | 50g | 20g | 8g |
| TS-1 HTS powder | 40g | 30g | 20g | 2g |
| Vinylbenzene | 20g | 30g | 70g | 100g |
| Divinylbenzene | 10g | 20g | 20g | 20g |
| Amylalcohol | 15g | 25g | 45g | 60g |
| Azo two isopropylcarbinol | 0.5g | 1.1g | 1.5g | 2g |
(2) cyclohexanone-oxime is prepared
Successively composite catalyst A7, composite catalyst A6, composite catalyst A5 and composite catalyst A4 being filled in diameter is 20 millimeters, length is in the fixed-bed reactor of 1200 millimeters, total filling volume is 50 milliliters, and the filling height ratio of composite catalyst A7, composite catalyst A6, composite catalyst A5 and composite catalyst A4 is 1: 1: 2: 2.Then, reaction raw materials (being made up of pimelinketone, hydrogen peroxide, ammonia and water) is injected fixed-bed reactor, reaction raw materials is flowed along the direction by composite catalyst A4 to composite catalyst A7, carry out cyclohexanone oxamidinating reaction, wherein, material rate is: the mol ratio of hydrogen peroxide and pimelinketone is 1.5: 1, and the mol ratio of ammonia and pimelinketone is 1.8: 1, and the volume ratio of pimelinketone and water is 8: 1; Reaction conditions is: temperature is 95 DEG C, and absolute pressure is 0.5MPa, and the volume space velocity of pimelinketone is 1h
-1.After successive reaction 100 hours, by analysis and calculate, pimelinketone transformation efficiency is 99.3%, and cyclohexanone-oxime selectivity is 99.6%.
Embodiment 3
The present embodiment is for illustration of the preparation method of described cyclohexanone-oxime of the present invention.
(1) composite catalyst is prepared
Prepare composite catalyst A8-A11 according to the method for embodiment 2 respectively, difference is, in preparation process, the ingredient proportion of Ti-MWW molecular sieve powder and TS-1 HTS powder is as shown in table 3 below.
Table 3
(2) cyclohexanone-oxime is prepared
Successively composite catalyst A11, composite catalyst A10, composite catalyst A9 and composite catalyst A8 being filled in diameter is 20 millimeters, length is in the fixed-bed reactor of 1200 millimeters, total filling volume is 50 milliliters, and the filling height ratio of composite catalyst A11, composite catalyst A10, composite catalyst A9 and composite catalyst A8 is 1: 1: 2: 2.Then, inject reaction raw materials according to the method for embodiment 2 and control reaction conditions, and the flow direction of reaction raw materials is for flow to composite catalyst A11 by composite catalyst A8.After successive reaction 100 hours, by analysis and calculate, pimelinketone transformation efficiency is 98.5%, and cyclohexanone-oxime selectivity is 98.9%.
Embodiment 4
The present embodiment is for illustration of the preparation method of described cyclohexanone-oxime of the present invention.
(1) composite catalyst is prepared
In polymerization reaction kettle, add Ti-MWW molecular sieve powder, TS-1 HTS powder, vinylbenzene, divinylbenzene and gasoline, after being uniformly mixed, during warming-in-water to 60 DEG C, add benzoyl peroxide, react 6 hours at 90 DEG C, obtain block composite catalyst, then carry out fragmentation and obtain the composite catalyst particulate that particle size is 1-3 millimeter, then 250 milliliters 1 is added, carry out swelling in 2-ethylene dichloride, keep swelling 5 hours at normal temperatures, pour out 1 afterwards, 2-ethylene dichloride, the dimethylbenzene adding 200 milliliters again carries out solvent extraction, extraction temperature is 55 DEG C, extraction times is 4 hours, repeat extracting three times, obtain the composite catalyst of HTS and resin.
Prepare composite catalyst A12 and A13 of HTS and resin respectively according to aforesaid method, and in respective preparation process, the charging capacity of material is as shown in table 4 below.
Table 4
| Composite catalyst A12 | Composite catalyst A13 | |
| Ti-MWW molecular sieve powder | 80g | 8g |
| TS-1 HTS powder | 20g | 2g |
| Vinylbenzene | 20g | 80g |
| Divinylbenzene | 10g | 40g |
| Gasoline | 15g | 60g |
| Benzoyl peroxide | 0.5g | 2g |
(2) cyclohexanone-oxime is prepared
Successively composite catalyst A13 and composite catalyst A12 being filled in diameter is 20 millimeters, and length is in the fixed-bed reactor of 1200 millimeters, and total filling volume is 50 milliliters, and the filling height ratio of composite catalyst A13 and composite catalyst A12 is 1: 2.Then, reaction raw materials (being made up of pimelinketone, hydrogen peroxide, ammonia and water) is injected fixed-bed reactor, reaction raw materials is flowed along the direction by composite catalyst A12 to composite catalyst A13, carry out cyclohexanone oxamidinating reaction, wherein, material rate is: the mol ratio of hydrogen peroxide and pimelinketone is 0.8: 1, and the mol ratio of ammonia and pimelinketone is 2.8: 1, and the volume ratio of pimelinketone and water is 2: 1; Reaction conditions is: temperature is 55 DEG C, and absolute pressure is 0.2MPa, and the volume space velocity of pimelinketone is 0.2h
-1.After successive reaction 100 hours, by analysis and calculate, pimelinketone transformation efficiency is 98.9%, and cyclohexanone-oxime selectivity is 99.1%.
As can be seen here, the preparation method of cyclohexanone-oxime according to the present invention can obtain higher pimelinketone transformation efficiency and cyclohexanone-oxime selectivity.
Claims (10)
1. the preparation method of a cyclohexanone-oxime, the method comprises: under cyclohexanone oxamidinating reaction conditions, make containing pimelinketone, ammonia, the reaction raw materials of hydrogen peroxide and solvent is by the multiple beds in fixed-bed reactor, each beds is all containing HTS and resin, along the flow direction of described reaction raw materials in reactor, in described beds, the content of described resin increases progressively, and the weight percentage of resin is less than 50% described at least part of described beds, wherein, the total height that the weight percentage of described resin is less than the beds of 50% is the 20-60% of the total height of described beds, described in adjacent two beds, the difference of the content of resin is 5 ~ 50 % by weight, described HTS contains Ti-MWW molecular sieve, described resin is the polymkeric substance of vinylbenzene and polyene-based compound, and the weight ratio of vinylbenzene and polyene-based compound is 2-5:1.
2. method according to claim 1, wherein, along the flow direction of described reaction raw materials in reactor, described in adjacent two beds, the difference of the content of resin is 10 ~ 30 % by weight.
3. method according to claim 1, wherein, along the flow direction of described reaction raw materials in reactor, the height of every layer of described beds is 0.5 ~ 95% of the total height of described beds.
4. method according to claim 3, wherein, along the flow direction of described reaction raw materials in reactor, the height of every layer of described beds is 2 ~ 50% of the total height of described beds.
5. method according to claim 1, wherein, described catalyst bed has 2 ~ 20 beds.
6. method according to claim 1, wherein, described cyclohexanone oxamidinating reaction conditions comprises: temperature of reaction is 55-95 DEG C, and reaction pressure is 0.1-0.5MPa, and during liquid, volume space velocity is 0.1-1h-1.
7. method according to claim 1, wherein, in described reaction raw materials, the mol ratio of hydrogen peroxide and pimelinketone is 0.8-1.5:1, and the mol ratio of ammonia and pimelinketone is 1.8-2.8:1, and the volume ratio of pimelinketone and described solvent is 1-10:1.
8. method according to claim 1, wherein, in described HTS, the content of Ti-MWW molecular sieve is more than 10 % by weight.
9. method according to claim 1, wherein, in described HTS, the content of Ti-MWW molecular sieve is more than 50 % by weight.
10. method according to claim 7, wherein, described solvent is water.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0384390A1 (en) * | 1989-02-21 | 1990-08-29 | Enichem Anic S.r.l. | Catalytic process for the preparation of oximes |
| CN102311363A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Ammoxidation method for cyclohexanone |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0384390A1 (en) * | 1989-02-21 | 1990-08-29 | Enichem Anic S.r.l. | Catalytic process for the preparation of oximes |
| CN102311363A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Ammoxidation method for cyclohexanone |
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